WO1994009315A1 - STAGED AIR, RECIRCULATING FLUE GAS LOW NOx BURNER - Google Patents

STAGED AIR, RECIRCULATING FLUE GAS LOW NOx BURNER Download PDF

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Publication number
WO1994009315A1
WO1994009315A1 PCT/US1993/009920 US9309920W WO9409315A1 WO 1994009315 A1 WO1994009315 A1 WO 1994009315A1 US 9309920 W US9309920 W US 9309920W WO 9409315 A1 WO9409315 A1 WO 9409315A1
Authority
WO
WIPO (PCT)
Prior art keywords
air
housing
bumer
fuel
flue gas
Prior art date
Application number
PCT/US1993/009920
Other languages
English (en)
French (fr)
Inventor
Andrew J. Syska
Charles E. Benson
Majed A. Togan
Donald P. Moreland
János Miklo's BEE'R
Original Assignee
Gas Research Institute, Inc.
Massachusetts Institute Of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gas Research Institute, Inc., Massachusetts Institute Of Technology filed Critical Gas Research Institute, Inc.
Priority to DE69303617T priority Critical patent/DE69303617T2/de
Priority to EP94901168A priority patent/EP0664871B1/de
Publication of WO1994009315A1 publication Critical patent/WO1994009315A1/en

Links

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C6/00Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion
    • F23C6/04Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection
    • F23C6/045Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection with staged combustion in a single enclosure
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C7/00Combustion apparatus characterised by arrangements for air supply
    • F23C7/02Disposition of air supply not passing through burner
    • F23C7/06Disposition of air supply not passing through burner for heating the incoming air
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C9/00Combustion apparatus characterised by arrangements for returning combustion products or flue gases to the combustion chamber
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2201/00Staged combustion
    • F23C2201/20Burner staging
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2202/00Fluegas recirculation
    • F23C2202/10Premixing fluegas with fuel and combustion air
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2900/00Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
    • F23C2900/06041Staged supply of oxidant
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2900/00Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
    • F23C2900/09002Specific devices inducing or forcing flue gas recirculation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/34Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery

Definitions

  • This invention relates to the field of gas-fired burners for furnaces and boilers and more particularly to burners for reducing NO x emission levels from combustion occurring in furnaces and boilers.
  • Such emissions include nitrogen oxides or NO x , primarily NO and NO 2 .
  • NO x emission levels should be significantly below 100 parts per million (ppm).
  • NO x emissions arise from nitrogen present in the combustion air and from fuel-bound nitrogen in coal or fuel oil if such fuels are burned. Conversion of fuel-bound nitrogen to
  • NO x depends on the amount and reactivity of the nitrogen compounds in the fuel and the amount of oxygen in the combustion zone. Conversion of fuel-bound nitrogen is not present in processes using fuels such as natural gas, which contain no fixed nitrogen compounds.
  • One way of reducing NO x content which has been effective in processes using nitrogen bearing fuels is to create a fuel-rich combustion zone followed by a fuel-lean combustion zone. This can be achieved by staging the introduction of air into the combustion chamber.
  • the fuel-rich zone contains less than the theoretical or stoichiometric amount of oxygen.
  • Recirculating flue gas into the flame is another technique to limit NO x emissions.
  • the recirculated flue gas reduces the oxygen concentration in the reactants and reduces the flame temperature by cooling the combustion products, thereby lowering NO x content.
  • NO x present in the recirculated flue gas can be f rther destroyed by rebuming.
  • the flue gases can also be used for other purposes, such as preheating the combustion air or vaporizing liquid fuels.
  • Burners which are particularly suitable for high temperature processes are disclosed in U.S. Patents Nos. 4,445,842 and 3,990,831. These burners incorporate an air driven jet pump for inducting flue gas into the air stream and to improve the mixing of the fuel, air, and flue gas. These burners also recirculate flue gases into the fuel/air mixture, which reduces
  • a low NO x , natural gas-fired burner for high temperature applications incorporating an air driven jet pump has been configured and optimized for the staged introduction of combustion air.
  • the burner comprises an air driven jet pump for mixing air, fuel, and recirculated flue gas and for forcing the mixture into the combustion chamber.
  • the burner includes an air inlet port which connects with a primary air passage for supplying combustion air to the jet pump and to provide a fuel-rich combustion zone.
  • the burner further includes a secondary air passage to provide a fuel-lean combustion zone downstream of the fuel-rich zone.
  • Fig. 1 is a cross-sectional view of a burner according to the present invention
  • Fig. 2 is a side view of the burner of Fig. 1;
  • Fig. 3 is an end view of the burner of Figs. 1 and 2;
  • Fig. 4 is a graph of NO x emissions vs. primary zone fuel equivalence ratio for a burner according to the present invention using combustion air at 260° C and flue gas at 700° C;
  • Fig. 5 is a graph of NO x emissions vs. primary zone fuel equivalence ratio for a burner according to the present invention using combustion air at 800° C and flue gas at 700° C;
  • Fig. 6 is a graph of NO x emissions vs. total flue gas recirculation for a burner according to the present invention
  • Fig. 7 is a graphical comparison of a burner according to the present invention and a commercial prior art burner showing NO x concentration along the axis of the burners
  • Fig. 8 is a graphical comparison of a burner according to the present invention and a commercial prior art burner showing temperature along the axis of the burners;
  • Fig. 9 is a graphical comparison of a burner according to the present invention and a commercial prior art burner showing heat extraction along the axis of the burners; .
  • Fig. 10 shows a fragmentary cross-sectional view of an alternative embodiment of a nozzle insert according to the present invention.
  • Fig. 11 is a cross-sectional view of an alternative embodiment of a burner according to the present invention.
  • a burner according to the preferred embodiment of the present invention is shown generally at 10 in Figures 1 and 2.
  • the burner 10 comprises a housing 12, a gaseous fuel connection 14, an air inlet connection 16, and a recirculating flue gas connection 18.
  • a fuel inlet nozzle 20 extends from the fuel connection 14 into the housing 12 through an opening in the housing end wall 22.
  • a fitting 24 is provided to seal the opening.
  • An observation port 26 is provided at the fuel connection 14.
  • the air inlet 16 communicates with an annular air chamber 30.
  • the air chamber communicates through annularly spaced openings 34 with primary air passage 32 and air nozzle 38.
  • the air chamber 30 also communicates with a plurality of annularly spaced axial secondary air passages 36.
  • the housing 12 comprises three sections: end section 40, mid section 42, and jet pump body 44.
  • the jet pump body 44 comprises a suction chamber portion 61, a mixing chamber portion 63, and a burner block or quarl 65.
  • a frustoconical suction chamber 60 is provided in the suction chamber portion 61.
  • a cylindrical mixing chamber 62 is provided in the mixing chamber portion 63.
  • a frustoconical dif ⁇ user 64 is provided in the burner block
  • the dif ⁇ user 64 also serves as a combustion chamber, to be more fully described below.
  • end and mid sections 40, 42 are interconnected by bolted annular flanges 46, 48.
  • the mid section 42 and jet pump body 44 are interconnected by bolted flanges 50,, 52.
  • An annular flange 54 is provided on jet pump body 44 for interconnection to a furnace wall 56, shown in Fig. 1.
  • the jet pump body 44 is interconnected to both the end section 40 and the mid section 42 by annular flange 68 between flanges 46 and 48.
  • the primary air openings 34 are provided in the annular flange 68.
  • the end and mid sections and the jet pump body may also be interconnected in any other suitable manner.
  • the burner housing may be connected to the furnace in any other suitable manner.
  • the end section 40 and mid section 42 are preferably fabricated from carbon steel 72 and lined with insulating castable material 74.
  • the jet pump body 44 is preferably fabricated from a high temperature dense refractory material 76 and an outer casing 78 of steel or cast iron.
  • a pilot light opening 80 and a scanner opening 82 are formed in the refractory material 76 surrounding the dif ⁇ user 64. In operation, air is forced under pressure through air inlet 16 into the annular chamber
  • the air stream divides in the annular chamber 30 into two streams, a primary air stream and a secondary air stream.
  • the primary air stream enters through the openings 34 into the primary air passage 32.
  • the passage 32 communicates via nozzle 38 with suction chamber 60. Air flowing through the nozzle 38 experiences a pressure drop. Natural gas fuel, entering through nozzle 20, concentric with air nozzle 38, also experiences a pressure drop. In flowing through the nozzle 38 and suction chamber 60, the lower pressure air and natural gas fuel cause flue gas, entering through inlet 18, to be drawn into the suction chamber.
  • the flue gas inlet 18 is connected tangentially to the housing mid section 42 to impart a spiral motion to the flue gas stream as it enters the primary air/fuel stream, which aids in maintaining flame stability.
  • the primary air and natural gas stream flows through the suction chamber 60 into the mixing chamber 62.
  • the primary air, fuel, and flue gas mix in the mixing chamber 62.
  • the mixture generally recovers some pressure in the mixing chamber and exits the mixing chamber 62 at a slightly increased pressure.
  • the mixed primary air, fuel, and flue gas then enter the diffuser 64 which has an increasing cross sectional area, by virtue of the frustoconical shape, to decrease the velocity and increase the pressure up to the pressure in the furnace.
  • the included angle of the diffuser becomes too large, the flow will break away into eddies, rather than expand. An included angle of approximately 18° has been found to be suitable.
  • a pilot flame provided through tube 80 ignites the air and fuel mixture in the dif ⁇ user 64.
  • the combustion can be observed through the scanner tube 82.
  • the secondary air stream enters the plurality of annularly spaced passages 36 from the air chamber 30 and passes through to the furnace, where it enters the periphery of the flame envelope, which extends from the diffuser into the furnace.
  • a fuel-rich primary combustion zone exists in the flame in and immediately outside the dif ⁇ user, which receives less than the theoretical amount of air, and a fuel-lean secondary combustion zone exists in the flame which extends into the furnace.
  • the flame in and immediately outside the diffusing section 64 may also be described as the primary flame, the flame in the furnace as the secondary flame.
  • N + OH --> NO + H The products HCN and NH will be partially converted in the fuel-rich flame to molecular nitrogen, N 2 , provided that the temperature is at least 1400 K and there is sufficient residence time for these reactions to go to completion.
  • the NO formed by the reaction of N 2 with hydrocarbon radicals or introduced with the flue gases can also be converted back to N 2 through a "reburn" route in the fuel-rich flame. This process is initiated by reactions producing HCN, for example,
  • the HCN further reacts to form N 2 at a rate that is dependent upon the fuel equivalence ratio and the temperature of the fuel-rich flame zone.
  • the jet pump configuration of the burner of the present invention introduces the fuel and primary air into the fuel-rich zone in a manner that extends the amount of recyclable flue gas which can be introduced before flame instability occurs.
  • flue gas recirculation is limited by the capacity of the jet pump more so than flame stability.
  • thermal NO formation is also reduced by the introduction of the secondary air jets from the secondary air passages 36.
  • the combustible products of the fuel-rich flame are intercepted in the furnace by the secondary air jets, which entrain burned and cooled combustion products before they mix with the products of the fuel-rich flame and bum as a secondary flame.
  • the peak temperature of the flame and the O 2 concentration are reduced, resulting in reduced thermal NO x formation.
  • the predetermined input or design parameters include the percent excess combustion air, fraction of primary air, and percent of recirculated flue gas.
  • the furnace conditions will determine the diffuser exit velocity and pressure. Both of these parameters affect the pressure drop through the primary air nozzle.
  • Other parameters determined by the application are the combustion air temperature, the flue gas temperature, and the fuel gas flow and temperature.
  • Important process and burner geometry parameters which are determined by the input parameters include the pressure drops through and diameters of the primary and secondary air nozzles and fuel nozzle and the diameter of the mixing chamber.
  • the pressure drops through the primary air nozzle and the gas fuel nozzle affect the ability of the jet pump to pull in the fuel and flue gas.
  • the supply of air is generally fixed.
  • the primary air nozzle diameter and mixing chamber must be carefully sized to optimize the efficiency of the jet pump based upon the predetermined primary air fraction, percent of flue gas recirculation, and furnace conditions.
  • the primary air nozzle diameter is generally sized to provide a pressure drop of 6 to 40 inches of water column, depending on the primary air flow and the amount of flue gas recirculation desired. Typically, the pressure drop will range between 4 and 24 inches of water column; in some applications, the pressure in the furnace is above atmospheric pressure, and the pressure drop through the primary air nozzle accordingly needs to be greater.
  • the individual diameters and the radial spacing of the secondary air passages 36 are also important parameters.
  • the passage exits are sized to produce a secondary air exit velocity between 50 and 300 actual feet per second and preferably between 150 and 200 actual feet per second.
  • a single secondary air passage could be provided if desired, a plurality of such passages spaced circumferentially about the diffuser is preferable.
  • the radial displacement of the secondary air passages ranges from 1.2 to 1.5 of the exit radius of the diffuser.
  • a further embodiment of the present invention contemplates nozzle inserts, which impart an angle between 0° and 90°.
  • the inserts comprise a first portion 92 which fits into the ends 94 of passages 36, which may be widened to better receive the inserts.
  • the inserts further comprise a second portion 96 which extends into the furnace, preferably angled toward the burner axis.
  • An angled passage 98 is provided in the insert to communicate with passage 36 and the furnace. The passages 98 are also angled toward the burner axis. In this manner, the secondary air stream passing through passage 36 is directed at an angle toward the flame envelope.
  • a 2.5 million BTU/hr test burner according to the present invention was built and operated. Fifty-two burner operating conditions were investigated. Parameters which were varied included the combustion air and recirculated flue gas temperatures, the percent primary and secondary air, and percent flue gas recirculation into the primary and secondary air streams. Intrusive probes were used to measure flame characteristics.
  • Fig. 4 is a graph of NO x emissions vs. primary zone fuel equivalence ratio, ⁇ , for a burner according to the present invention using combustion air at 260° C and flue gas at 700° C.
  • the fuel equivalence ratio, ⁇ is the ratio of stoichiometric O 2 to O 2 supplied.
  • the approximate percent of primary air supplied, assuming no oxygen in the recirculated flue gas, is also indicated on Fig.
  • Fig. 4 is a graph of NO x emissions vs.
  • the primary zone fuel equivalence ratio for a bumer according to the present invention using combustion air preheated to 800°C and recirculated flue gas at 700°C.
  • staging the combustion air significantly reduced NO x emissions.
  • NO x emission level was approximately 150 ppm.
  • FIG. 6 A comparison of the results of staged air versus unstaged air is shown in Fig. 6, which is taken from the data shown in Figs. 4 and 5.
  • Fig. 6 also shows the NO x emissions using staged and unstaged air at a combustion air temperature of 260° C. At this air temperature, little difference in NO x production was observed due to air staging.
  • the bumer of the present invention was compared to a prior art commercially available bumer, a TRANSJET bumer.
  • the TRANSJET bumer was chosen since it represents a state of the art commercially available low NO x bumer capable of operating with preheated combustion air. Both burners were fired at the rate of 2.51 million BTU/hr (735 kW). The test results of this comparison are shown in Tables 1 and 2 and in Figs. 7, 8, and 9.
  • Table 1 and Fig. 7 present NO x concentration per axial distance from the bumer exit.
  • the NO x concentration remained lower for the bumer of the present invention than that of the
  • NO x emissions from the bumer of the present invention ranged from 24 to 45 ppm, while NO x emissions for the prior art bumer ranged from 160 to over 200 ppm.
  • Table 1 and Fig. 8 present the temperature vs. axial distance from the bumer exit. As can be seen, the temperature remained lower for the bumer of the present invention. Also, the temperature at the exit of the primary combustion zone is about 1300° C, rising to a peak of only about 1400° C in the secondary combustion zone. These temperatures are below the threshold temperatures at which NO x formation becomes significant. The narrow, pencil-like shape of the prior art bumer produced higher flame temperatures and NO x .
  • Figure 8 also shows that the temperature for the burner of the present invention is relatively uniform, with an absence of hot spots, which also contributes to low NO x emissions. Further, a uniform flame temperature is important in many industrial heating applications, such as forging or reheating.
  • Table 2 and Fig. 9 present heat extraction to the furnace wall per axial distance from the bumer exit. Heat extraction using the bumer of the present invention remained competitive with heat extraction using the prior art bumer: 178 kW for the present invention, 172 kW for the prior art bumer.
  • Rapid burning results which, for the pencil-like geometry of the flame of the prior art burner, leads to a rapid temperature increase of the flame.
  • the temperature increase leads to a jump in the thermal NO x level to over 200 ppm.
  • the combustion process begins in the diffusing section of the bumer.
  • Fig. 11 An alternative embodiment of the present invention is shown in Fig. 11.
  • flue gas is also recirculated into the secondary combustion zone with the secondary air.
  • the bumer 110 comprises a housing 112, a gaseous fuel connection 114, a primary air inlet connection 116, and a primary recirculating flue gas connection 118.
  • a fuel inlet nozzle 120 extends from the fuel connection 114 into the housing 112 within the air nozzle 138.
  • a jet pump 144 is formed within the housing 112.
  • the jet pump comprises a suction chamber 160, a cylindrical mixing chamber 162, and a frustoconical diffuser 164.
  • the primary air and fuel supplied under pressure and passing through the nozzle 138 creates a suction which pulls in the primary flue gas.
  • the diffuser 64 serves as the primary combustion chamber.
  • a secondary air inlet 117 and nozzle 139 are also provided on the housing 112.
  • a secondary recirculating flue gas connection 119 is provided adjacent to the secondary air inlet 117.
  • the secondary air inlet 117 and secondary flue gas inlet communicate with a plurality of annularly spaced passages 136 spaced about the dif ⁇ user 164.
  • the passages 136 introduce the secondary air and flue gas into the secondary combustion zone in the furnace.
  • the burner has been described in conjunction with gaseous fuels.
  • Axial injection of the gaseous fuel, as shown in Fig. 1, is preferable, although radial or tangential injection may be provided if desired. Radial or tangential injection ports may be provided in the suction chamber or mixing chamber.
  • the bumer may also be configured for liquid fuels, although such fuels must first be vaporized.
  • the fuels may be vaporized by mixing with the flue gas, for example, as shown in Patent No. 3,990,831.
  • the vaporized fuel may then be drawn into the air stream by the air driven jet pump along with the flue gas.
  • the bumer in this invention allows the combustion process to begin in the diffusing section of the bumer.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
PCT/US1993/009920 1992-10-16 1993-10-15 STAGED AIR, RECIRCULATING FLUE GAS LOW NOx BURNER WO1994009315A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE69303617T DE69303617T2 (de) 1992-10-16 1993-10-15 BRENNER ZUR NOx-ARMEN VERBRENNUNG MIT GESTUFTER LUFTZUFUHR UND ABGASRÜCKFÜHRUNG
EP94901168A EP0664871B1 (de) 1992-10-16 1993-10-15 BRENNER ZUR NOx-ARMEN VERBRENNUNG MIT GESTUFTER LUFTZUFUHR UND ABGASRÜCKFÜHRUNG

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/964,550 1992-10-16
US07/964,550 US5269679A (en) 1992-10-16 1992-10-16 Staged air, recirculating flue gas low NOx burner

Publications (1)

Publication Number Publication Date
WO1994009315A1 true WO1994009315A1 (en) 1994-04-28

Family

ID=25508689

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US1993/009920 WO1994009315A1 (en) 1992-10-16 1993-10-15 STAGED AIR, RECIRCULATING FLUE GAS LOW NOx BURNER
PCT/US1993/009965 WO1994009316A1 (en) 1992-10-16 1993-10-15 METHOD OF BURNING GAS IN A STAGED AIR, RECIRCULATING FLUE GAS LOW NOx BURNER

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US1993/009965 WO1994009316A1 (en) 1992-10-16 1993-10-15 METHOD OF BURNING GAS IN A STAGED AIR, RECIRCULATING FLUE GAS LOW NOx BURNER

Country Status (5)

Country Link
US (1) US5269679A (de)
EP (2) EP0663989B1 (de)
AT (2) ATE140309T1 (de)
DE (2) DE69303617T2 (de)
WO (2) WO1994009315A1 (de)

Cited By (1)

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WO1994009316A1 (en) 1994-04-28
EP0663989B1 (de) 1996-07-10
ATE140309T1 (de) 1996-07-15
DE69303613T2 (de) 1997-03-06
DE69303613D1 (de) 1996-08-14
EP0664871B1 (de) 1996-07-10
EP0664871A1 (de) 1995-08-02
US5269679A (en) 1993-12-14
DE69303617D1 (de) 1996-08-14
EP0663989A1 (de) 1995-07-26
DE69303617T2 (de) 1998-01-29
ATE140310T1 (de) 1996-07-15

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